CN111326716A - Multi-element co-doped active carbon composite material for negative electrode of lead-carbon battery, preparation method of multi-element co-doped active carbon composite material and lead-carbon battery - Google Patents

Multi-element co-doped active carbon composite material for negative electrode of lead-carbon battery, preparation method of multi-element co-doped active carbon composite material and lead-carbon battery Download PDF

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CN111326716A
CN111326716A CN201811528279.5A CN201811528279A CN111326716A CN 111326716 A CN111326716 A CN 111326716A CN 201811528279 A CN201811528279 A CN 201811528279A CN 111326716 A CN111326716 A CN 111326716A
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composite material
active carbon
doped
activated carbon
hydrogen evolution
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CN111326716B (en
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张聪
郑申棵
赵永彬
马立军
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Shandong Obo New Material Co ltd
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Shandong Obo New Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a multi-element co-doped active carbon composite material, which comprises active carbon and a hydrogen evolution inhibiting heteroatom doped on the active carbon; the hydrogen evolution inhibiting heteroatoms are two or three of N, P and F; the hydrogen evolution inhibiting heteroatom is provided by a heteroatom compound. The invention adopts the heteroatom compound as a source for inhibiting hydrogen evolution atoms, simultaneously dopes two or three kinds of hydrogen evolution inhibiting heteroatoms, has rich phosphorus, nitrogen and fluorine elements, and can be used as a phosphorus source, a nitrogen source and a fluorine source. Heteroatom compounds are added in the process of preparing the activated carbon, the mixture is pyrolyzed at the same time of high-temperature activation in one step, the multi-element doped activated carbon is obtained, the preparation process is simplified, various heteroatoms can be uniformly dispersed on the surface and in pore channels of the activated carbon, the function of inhibiting hydrogen evolution is effectively improved, lone pair electrons on the heteroatoms can increase the charge density of the carbon material, and thus the conductivity and the wettability of an electrolyte solution are increased.

Description

Multi-element co-doped active carbon composite material for negative electrode of lead-carbon battery, preparation method of multi-element co-doped active carbon composite material and lead-carbon battery
Technical Field
The invention belongs to the technical field of lead-carbon materials, and relates to a multi-element co-doped activated carbon composite material and a preparation method thereof, and a lead-carbon battery, in particular to a multi-element co-doped activated carbon composite material for a negative electrode of a lead-carbon battery, a preparation method thereof, and a lead-carbon battery.
Background
With the continuous progress of scientific technology, the market scale of the global energy storage battery is rapidly increased. Lead-acid batteries have significant advantages in terms of cost performance, safety, low temperature performance, production and recovery processes, and have become the battery type with the greatest global market share. However, the development and application of lead-acid batteries are limited by the defects of low specific energy, large volume, difficult rapid charging, short cycle life (300-800 times) and the like of the lead-acid batteries. With the maturity and application of lithium battery technology, lithium batteries are gradually replacing the market status of lead-acid batteries, and the lead-acid batteries must be improved and upgraded to improve the performance of the batteries to face the challenge. Among them, new technologies such as corrosion-resistant alloy grids, gel batteries, lead-carbon batteries, super batteries, etc. have been developed.
The lead-carbon battery is a new technology for the development of lead-acid batteries, and has great improvement in the rate and cycle life. The lead-carbon battery can be directly produced on a lead-acid battery production line without modification and upgrading by adding the activated carbon into a negative active material Pb of the lead-acid battery. The lead-carbon battery has the advantages of instantaneous high-rate charge and discharge of the super capacitor and the specific energy of the lead-acid battery. In the high-rate discharge process, the carbon negative electrode can share part of current on the lead negative electrode, so that the irreversible sulfation phenomenon of the battery negative electrode can be effectively inhibited, and the service life of the battery is prolonged. Meanwhile, in the high-rate charging process, the carbon negative electrode can play a role of a buffer, and impact of large current on the lead negative plate is dispersed, so that the charging acceptance of the battery is improved. Although the cycle life and the charge-discharge rate of the lead-carbon battery are greatly improved, the lead-carbon battery also faces a new problem, the carbon material is a low hydrogen evolution overpotential material, and a serious hydrogen evolution phenomenon is easily generated under the condition of normal charge and discharge of the battery, so that the dehydration and the dryness of electrolyte are accelerated, the battery is invalid, and the service life of the lead-carbon battery is seriously influenced. Therefore, hydrogen evolution is a key problem which cannot be avoided in the development and application process of the lead-carbon battery.
Conventionally, an oxide having a high hydrogen potential (a compound of indium oxide, tin dioxide, silver oxide, or zinc) or other atoms (N, S, P, F, or the like) is added to a carbon material to suppress a hydrogen evolution phenomenon of the carbon material. However, the hydrogen evolution inhibitor is simply and mechanically mixed with the activated carbon and the lead powder, in-situ doping is not realized, the addition amount of the modifier is only 0.05-5% of that of the lead powder, the modifier is rarely in actual contact with the activated carbon, and the influence mechanism of the modifier on the improvement of the hydrogen evolution potential of the activated carbon is greatly weakened, so that the problem of water loss of the lead-carbon battery is not effectively solved by simply adding the hydrogen evolution inhibitor; the preparation method of the activated carbon with the surface doped with atoms takes the activated carbon as a raw material, and is doped by adding other atomic compounds, so that the preparation is complex, the cost of the activated carbon is high, and the hydrogen evolution inhibiting effect caused by single doped element of the activated carbon is poor.
Therefore, how to better solve the problem of hydrogen evolution of the lead-carbon battery and exert the performance of the activated carbon is one of the key challenges faced by many developers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a multi-element co-doped activated carbon composite material and a preparation method thereof, and a lead-carbon battery, particularly a multi-element co-doped activated carbon composite material for a negative electrode of a lead-carbon battery and a preparation method thereof.
The invention provides a multi-element co-doped active carbon composite material, which comprises active carbon and a hydrogen evolution inhibiting heteroatom doped on the active carbon;
the hydrogen evolution inhibiting heteroatoms are two or three of N, P and F;
the hydrogen evolution inhibiting heteroatom is provided by a heteroatom compound.
Preferably, the heteroatom compound is a nitrogen-phosphorus-containing compound and/or a fluorine-containing nitrogen-phosphorus-containing compound;
in the composite material, the mass percentage of the nitrogen atoms is 0.1-10%;
in the composite material, the mass percentage of the phosphorus atoms is 0.1-10%;
in the composite material, the mass percentage of the fluorine atoms is 0.1-10%.
Preferably, the heteroatom compound is a phosphazene compound;
the composite material is obtained by activating a precursor of activated carbon and a heteroatom compound;
the particle size of the multi-element co-doped active carbon composite material is 5-50 mu m;
the specific surface area of the multi-element co-doped active carbon composite material is 500-1500 m2/g。
Preferably, the heteroatom compound comprises one or more of hexamethylcyclotriphosphazene, trimerization cyclophosphazene, hexamethoxycyclotriphosphazene, hexaethoxy cyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoroethoxy cyclotriphosphazene and pentafluorophenoxy cyclotriphosphazene;
the hydrogen evolution inhibiting hetero atoms are doped on the surface of the activated carbon and are uniformly doped in pore channels of the activated carbon;
the precursor of the activated carbon comprises one or more of petroleum coke, biomass and resin;
the multi-element co-doped active carbon composite material has a hydrogen evolution current density of 0.5-1.5A/g when the hydrogen evolution potential is-0.9V.
Preferably, the heteroatom compound comprises hexamethylcyclotriphosphazene, trimerization cyclophosphazene, hexamethoxycyclotriphosphazene, hexaethoxy cyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoroethoxy cyclotriphosphazene or pentafluorophenoxy cyclotriphosphazene;
the mesoporous volume of the multi-element co-doped active carbon composite material is 50-80%;
the contact angle of water drops of the multi-element co-doped active carbon composite material is less than or equal to 15 degrees;
the conductivity of the multi-element co-doped active carbon composite material is more than or equal to 50S/cm.
The invention also provides a preparation method of the multi-element co-doped active carbon composite material, which comprises the following steps:
1) grinding and mixing the activated carbon precursor and the heteroatom compound to obtain a mixed material;
2) and mixing the mixed material obtained in the step with an activating agent again, and activating under the condition of protective gas to obtain the multi-element co-doped active carbon composite material.
Preferably, the milling mixing comprises ball milling dispersion;
the grinding and mixing time is 0.5-2 h;
the rotation speed of the grinding and mixing is 100-800 r/min;
the mass ratio of the heteroatom compound to the activated carbon precursor is 1: (5-30).
Preferably, the method also comprises a jet milling step after the mixing;
the activator comprises one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide and zinc chloride;
the mass ratio of the activating agent to the activated carbon precursor is (1-6): 1.
preferably, the remixing time is 0.5-2 h;
the activation temperature is 400-800 ℃;
the activation time is 1-6 h;
a post-treatment step is also included after the activation;
the post-treatment step comprises one or more of impurity removal, filtration, washing and drying.
The invention also provides a lead-carbon battery, which comprises a positive electrode and a negative electrode;
the cathode comprises the multielement co-doped active carbon composite material prepared by the preparation method of any one of the above technical schemes or the multielement co-doped active carbon composite material prepared by the preparation method of any one of the above technical schemes.
The invention provides a multi-element co-doped active carbon composite material, which comprises active carbon and a hydrogen evolution inhibiting heteroatom doped on the active carbon; the hydrogen evolution inhibiting heteroatoms are two or three of N, P and F; the hydrogen evolution inhibiting heteroatom is provided by a heteroatom compound. Compared with the prior art, the method aims at solving the problem of hydrogen evolution of the lead-carbon battery in the prior art that the hydrogen evolution inhibitor, the active carbon and the lead powder are simply and mechanically mixed without in-situ doping, the addition amount of the modifier is small, the actual contact between the modifier and the active carbon is very small, and the influence mechanism of the modifier on the improvement of the hydrogen evolution potential of the active carbon is greatly weakened; the preparation method of the activated carbon with the surface doped with other atoms has the defects of complex preparation process, higher cost and poor hydrogen evolution inhibition effect caused by single doped element.
The invention provides a multi-element co-doped active carbon composite material, and aims to solve the problems that in the prior art, a plurality of elements are doped simultaneously, but a plurality of heteroatom raw materials are required to be added independently, the operation is still complex, and the cost is high. The invention creatively adopts the heteroatom compound as a source for inhibiting hydrogen evolution atoms, and simultaneously dopes two or three kinds of hydrogen evolution inhibiting heteroatoms, and the heteroatom compound has rich phosphorus, nitrogen and fluorine elements, and can be used as a phosphorus source, a nitrogen source and a fluorine source. Heteroatom compounds are added in the process of preparing the activated carbon from petroleum coke and biomass raw materials, the mixture is pyrolyzed at the same time of high-temperature activation in one step, the multi-element (N, P and F) doped activated carbon is successfully obtained, the preparation process is simplified, various heteroatoms can be uniformly dispersed on the surface and in pore channels of the activated carbon, the function of inhibiting hydrogen evolution is effectively improved, and lone-pair electrons carried by the heteroatoms can increase the charge density of the carbon material, so that the conductivity and the wettability of an electrolyte solution are increased. Therefore, the realization of the multi-element co-doping of the activated carbon is beneficial to the application of the activated carbon in the field of lead-carbon batteries and has profound significance.
The multi-element co-doped active carbon composite material provided by the invention has the advantages of uniform doping elements, simple and efficient preparation process and low cost, is favorable for the application of active carbon in the field of lead-carbon batteries, and is more suitable for popularization and application of industrial mass production.
Experimental results show that the multielement co-doped active carbon composite material provided by the invention has high content of nitrogen, phosphorus and fluorine elements, can effectively inhibit hydrogen evolution, and has improved wettability and conductivity of the active carbon, wherein the pore volume ratio is 50-80%, the contact angle of a water drop can reach 0 degree, and the conductivity can reach 80S/cm.
Drawings
FIG. 1 is an SEM scanning electron micrograph of nitrogen and phosphorus co-doped activated carbon prepared in example 1 of the present invention;
FIG. 2 is an SEM scanning electron micrograph of nitrogen and phosphorus co-doped activated carbon prepared in example 2 of the present invention;
fig. 3 is an SEM scanning electron micrograph of the nitrogen-phosphorus-fluorine co-doped activated carbon prepared in example 3 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably adopts the conventional purity used in the field of analytical purification or lead carbon batteries.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a multi-element co-doped active carbon composite material, which comprises active carbon and a hydrogen evolution inhibiting heteroatom doped on the active carbon;
the hydrogen evolution inhibiting heteroatoms are two or three of N, P and F;
the hydrogen evolution inhibiting heteroatom is provided by a heteroatom compound.
The source of the activated carbon is not particularly limited in the present invention, and may be any source of activated carbon known to those skilled in the art, and those skilled in the art can select and adjust the source according to the actual application, the product requirement and the quality requirement, and the precursor of the activated carbon of the present invention preferably includes one or more of petroleum coke, biomass and resin, and more preferably petroleum coke, biomass or resin.
The selection of the heteroatom compound is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application condition, the product requirement and the quality requirement, in order to ensure one-step uniform doping of multiple elements, improve the effect of inhibiting hydrogen evolution and simultaneously increase the conductivity and wettability, the heteroatom compound is preferably a nitrogen-containing phosphorus compound and/or a fluorine-containing nitrogen phosphorus compound, more preferably a nitrogen-containing phosphorus compound or a fluorine-containing nitrogen phosphorus compound, and particularly is selected to be a phosphazene compound (phosphazene and a derivative thereof), specifically one or more of hexamethylcyclotriphosphazene, trimeric cyclotriphosphazene, hexamethoxycyclotriphosphazene, hexaethoxycyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene and pentafluorophenoxycyclotriphosphazene, more specifically to be hexamethylcyclotriphosphazene, trimeric cyclotriphosphazene, trimeric cyclotriphosphazen, Hexamethoxycyclotriphosphazene, hexaethoxycyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene or pentafluorophenoxycyclotriphosphazene.
In the present invention, the hydrogen evolution inhibiting hetero atom is two or three of N, P and F, more preferably two of N and P, or N, P and F. The content of the hydrogen evolution inhibiting heteroatom is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application situation, the product requirement and the quality requirement, in order to ensure one-step uniform doping of multiple elements, improve the hydrogen evolution inhibiting effect and increase the conductivity and wettability, the mass percentage of the nitrogen atom in the composite material is preferably 0.1-10%, more preferably 0.5-8%, more preferably 1-6%, and more preferably 2-5%. In the composite material, the content of the phosphorus atoms by mass is preferably 0.1% to 10%, more preferably 0.5% to 8%, more preferably 1% to 6%, and more preferably 2% to 5%. . In the composite material, the fluorine atom content by mass is preferably 0.1% to 10%, more preferably 0.5% to 8%, more preferably 1% to 6%, and more preferably 2% to 5%. .
The method for providing the heteroatom compound for inhibiting hydrogen evolution has no particular limitation in principle, and a person skilled in the art can select and adjust the method according to the actual application condition, the product requirement and the quality requirement. In order to ensure the performance of the final composite material, in the multi-element co-doped active carbon composite material, the hydrogen evolution inhibiting hetero atoms are not only doped on the surface of the active carbon, but also uniformly doped in the pore channels of the active carbon.
The performance and parameters of the multi-element co-doped active carbon composite material are not particularly limited, and a person skilled in the art can select and adjust the multi-element co-doped active carbon composite material according to the actual application situation, the product requirements and the quality requirements, the multi-element co-doped active carbon composite material provided by the invention has multiple excellent performances, and the particle size of the multi-element co-doped active carbon composite material is preferably 5-50 μm, more preferably 15-40 μm, and more preferably 25-30 μm. When the hydrogen evolution potential is-0.9V, the hydrogen evolution current density of the multi-element co-doped active carbon composite material can be 0.5-1.5A/g, also can be 0.7-1.3A/g, and also can be 0.9-1.1A/g. Said pluralityThe specific surface area of the element co-doped active carbon composite material can be 500-1500 m2(iii) the molar ratio of the molar ratio may be 700 to 1300m2A ratio of 900 to 1100 m/g2(ii) in terms of/g. The mesoporous volume of the multi-element co-doped active carbon composite material can be 50-80%, 55-75% or 60-70%. The contact angle of a water drop of the multielement codoped activated carbon composite material is preferably less than or equal to 15 degrees, more preferably less than or equal to 10 degrees, and more preferably less than or equal to 5 degrees. The conductivity of the multi-element co-doped activated carbon composite material is preferably equal to or greater than 50S/cm, more preferably equal to or greater than 60S/cm, more preferably equal to or greater than 70S/cm, and more preferably equal to or greater than 80S/cm.
The invention also provides a preparation method of the multi-element co-doped active carbon composite material, which comprises the following steps:
1) grinding and mixing the activated carbon precursor and the heteroatom compound to obtain a mixed material;
2) and mixing the mixed material obtained in the step with an activating agent again, and activating under the condition of protective gas to obtain the multi-element co-doped active carbon composite material.
The selection, composition and structure of the materials in the preparation method and the corresponding preferred principle of the invention can preferably correspond to the selection, composition and structure of the multi-element co-doped active carbon composite material and the corresponding preferred principle, and are not described in detail herein.
Firstly, grinding and mixing an active carbon precursor and a heteroatom compound to obtain a mixed material.
The selection and parameters of the activated carbon precursor are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the practical application, product requirements and quality requirements, and the activated carbon precursor of the present invention preferably includes one or more of petroleum coke, biomass and resin, and more preferably petroleum coke, biomass or resin.
In the invention, the adding amount of the heteroatom compound is not particularly limited in principle, and a person skilled in the art can select and adjust the adding amount according to the actual application condition, the product requirement and the quality requirement, in order to ensure one-step uniform doping of multiple elements, improve the effect of inhibiting hydrogen evolution and simultaneously increase the conductivity and wettability, the mass ratio of the heteroatom compound to the activated carbon precursor is preferably 1: (5-30), more preferably 1: (8-28), more preferably 1: (10-25), more preferably 1: (15-20).
The method is characterized in that the grinding and mixing mode and parameters are not particularly limited in principle, and a person skilled in the art can select and adjust the grinding and mixing mode and the parameters according to the actual application condition, the product requirement and the quality requirement. The time for grinding and mixing is preferably 0.5-2 h, more preferably 0.7-1.8 h, and more preferably 1.0-1.5 h. The rotation speed of the grinding and mixing is preferably 100-800 r/min, more preferably 200-700 r/min, and more preferably 400-500 r/min.
In order to ensure one-step uniform doping of multiple elements and improve the effect of inhibiting hydrogen evolution, the invention integrates and refines the process flow, and preferably also comprises a jet milling step after mixing. According to the invention, the mixed material with a specific particle size is obtained through the steps, and the particle size of the mixed material is preferably 5-50 μm, more preferably 15-40 μm, and more preferably 25-30 μm.
According to the invention, the mixed material obtained in the above step is mixed with an activating agent again, and then activated under the condition of protective gas, so as to obtain the multi-element co-doped active carbon composite material.
The selection of the activating agent is not particularly limited in principle by the present invention, and may be selected and adjusted by those skilled in the art according to the practical application, product requirements and quality requirements, and in order to ensure one-step uniform doping of multiple elements, improve the hydrogen evolution inhibition effect, and increase the conductivity and wettability, the activating agent preferably comprises one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide and zinc chloride, and more preferably potassium hydroxide, sodium hydroxide, calcium hydroxide or zinc chloride.
The addition amount of the activating agent is not particularly limited in principle, and a person skilled in the art can select and adjust the activating agent according to the actual application condition, the product requirement and the quality requirement, in order to ensure one-step uniform doping of multiple elements, improve the effect of inhibiting hydrogen evolution and increase the conductivity and wettability, the mass ratio of the activating agent to the activated carbon precursor is preferably (1-6): 1, more preferably (2-5): 1, more preferably (3-4): 1.
the protective gas is not particularly limited in the present invention, and may be any protective gas known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the protective gas of the present invention preferably includes one or more of nitrogen and inert gas, and more preferably nitrogen or argon.
The invention is not limited to the specific mixing method and parameters, and the conventional mixing method and parameters known to those skilled in the art can be used, and those skilled in the art can select and adjust the mixing method according to the actual application situation, the product requirement and the quality requirement, and the mixing method of the invention is preferably stirring mixing. The remixing time of the invention is preferably 0.5-2 h, more preferably 0.7-1.8 h, and more preferably 1.0-1.5 h.
The activation conditions are not particularly limited in principle, and the petroleum coke activation conditions known by the technical personnel in the field can be selected and adjusted according to the actual production situation, the product requirements and the quality requirements, the activation temperature is preferably 400-800 ℃, more preferably 450-750 ℃, more preferably 500-700 ℃, and more preferably 550-650 ℃ in order to ensure one-step uniform doping of multiple elements, improve the effect of inhibiting hydrogen evolution and increase the conductivity and wettability. The activation time is preferably 1-6 h, more preferably 2-5 h, and more preferably 3-4 h.
In order to further improve the one-step uniform doping of multiple elements and better improve the effect of inhibiting hydrogen evolution, the process route is integrated and refined, and the post-treatment step is preferably included after the activation. The post-treatment step preferably comprises one or more of impurity removal, filtration, washing and drying, more preferably acid washing impurity removal, water washing and drying. The post-treatment of the invention preferably comprises the following specific steps:
and removing an activating agent and impurities in the composite carbon material by using dilute acid, washing the composite carbon material to be neutral by using deionized water, and drying the composite carbon material after washing. The acid for pickling according to the present invention is preferably one or more of hydrochloric acid, nitric acid, and phosphoric acid, and more preferably hydrochloric acid, nitric acid, or phosphoric acid.
According to the invention, the phosphazene compound and the activated carbon precursor are subjected to ball milling pre-dispersion, then subjected to airflow crushing, and then uniformly mixed with the activating agent for co-activation, so that various heteroatoms are uniformly distributed on the surface and in the pore channels of the activated carbon, the hydrogen evolution potential, the wettability and the conductivity of the activated carbon are remarkably improved, and the problems brought by the traditional activated carbon are effectively solved. And the cost is low, the process is simple, the use is convenient, and the industrial production is easy.
The invention also provides a lead-carbon battery, which comprises a positive electrode and a negative electrode. The cathode comprises the multielement co-doped active carbon composite material prepared by the preparation method of any one of the above technical schemes or the multielement co-doped active carbon composite material prepared by the preparation method of any one of the above technical schemes. The definition of the lead carbon battery in the present invention is not particularly limited, and may be defined as a lead carbon battery well known to those skilled in the art.
The steps of the invention provide a multi-element co-doped active carbon composite material for a lead-carbon battery cathode, a preparation method thereof and a lead-carbon battery, wherein a phosphazene compound is used as a source for inhibiting hydrogen evolution atoms, two or three kinds of heteroatoms for inhibiting hydrogen evolution are doped simultaneously, the raw material source is wide, the functions are various, the phosphazene compound can provide various heteroatoms, has rich phosphorus, nitrogen and fluorine elements, and can be used as a phosphorus source, a nitrogen source and a fluorine source. The invention adds heteroatom compound in the process of preparing active carbon from precursor, through special mixing process and particle size, the two are uniformly compounded, then the mixture is pyrolyzed in one step while being activated at high temperature, and the multi-element (N, P, F) doped active carbon is obtained.
The invention carries out doping in the preparation process of the activated carbon without modification and upgrade, not only simplifies the preparation process and has simple process, but also can uniformly disperse various heteroatoms on the surface and in pore channels of the activated carbon, effectively improves the function of inhibiting hydrogen evolution, and simultaneously increases the charge density of the carbon material by lone pair electrons carried by the heteroatoms, thereby increasing the conductivity and the wettability of an electrolyte solution. Therefore, the method realizes the multi-element co-doping of the activated carbon, is favorable for the application of the activated carbon in the field of lead-carbon batteries, and has profound significance.
The multi-element co-doped active carbon composite material provided by the invention has the advantages of uniform doping elements, simple and efficient preparation process and low cost, is favorable for the application of active carbon in the field of lead-carbon batteries, and is more suitable for popularization and application of industrial mass production.
Experimental results show that the multielement co-doped active carbon composite material provided by the invention has high content of nitrogen, phosphorus and fluorine elements, can effectively inhibit hydrogen evolution, and has improved wettability and conductivity of the active carbon, wherein the pore volume ratio is 50-80%, the contact angle of a water drop can reach 0 degree, and the conductivity can reach 80S/cm.
For further illustration of the present invention, the multi-element co-doped activated carbon composite material, the preparation method thereof, and the lead carbon battery provided by the present invention are described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Weighing 6g of hexamethyl-trimeric phosphazene and 100g of petroleum coke, performing ball milling pre-dispersion, crushing a pre-dispersion mixture to a particle size D50 of 15 mu m by using a jet mill, mixing the crushed material and an activating agent potassium hydroxide according to a mass ratio of 1:3, heating to 700 ℃ in an activation furnace with nitrogen protection after uniform mixing, performing activation treatment for 2 hours, cooling to room temperature after reaction is finished, removing the activating agent and impurities in the obtained carbon material by using dilute hydrochloric acid, washing to be neutral by using deionized water, and drying after washing to obtain the nitrogen-phosphorus co-doped activated carbon.
The nitrogen and phosphorus co-doped activated carbon prepared in example 1 of the present invention was characterized.
Referring to fig. 1, fig. 1 is an SEM scanning electron micrograph of the nitrogen and phosphorus co-doped activated carbon prepared in example 1 of the present invention.
BET test is carried out on the doped active carbon, and the result shows that the specific surface area of the co-doped active carbon is 1700m2/g。
XPS test of the doped active carbon shows that the mass percent of nitrogen atoms and phosphorus atoms doped in the co-doped active carbon is 1.42% and 2.37%.
The nitrogen and phosphorus co-doped activated carbon prepared in the embodiment 1 of the invention is subjected to electrochemical performance detection.
Weighing the multi-element co-doped active carbon prepared in the embodiment, a conductive agent and a binder according to a mass ratio of 8:1:1, uniformly mixing, dripping isopropanol in a mortar grinding process until the mixture is pasty and has no dry powder, coating the mixture on a titanium sheet current collector, drying the titanium sheet current collector for 6 hours in vacuum at 120 ℃ to be used as a working electrode, wherein the auxiliary electrode is 1 × 1cmPt, and the reference electrode is Hg/Hg2SO4Electrode and electrolyte are 5mol/LH2SO4And carrying out LSV test on the three-electrode system by adopting a Zahner electrochemical workstation, wherein the LSV test scanning speed is 10mV/s, and the voltage window is-1.35 to-0.5V.
According to LSV curve analysis, the hydrogen evolution potential of the activated carbon prepared in parallel without doping with the same raw material is-0.85V, and when the potential is-1.35V, the hydrogen evolution current density of the activated carbon prepared in parallel without doping with the same raw material is 8.46A/g; the hydrogen evolution potential of the nitrogen and phosphorus co-doped active carbon prepared in the above embodiment is shifted from minus 0.85V to minus 1.06V, and the hydrogen evolution current density at minus 1.35V is 0.725A/g, which indicates that the nitrogen and phosphorus co-doped active carbon prepared in the above embodiment has an obvious hydrogen evolution inhibition effect.
Other performance tests were performed on the nitrogen-phosphorus co-doped activated carbon prepared in example 1 of the present invention.
The conductivity of the activated carbon was 30S/cm as measured by a powder resistance meter.
The wettability of the activated carbon is tested by testing a contact angle, and the specific method comprises the following steps:
at 20 deg.C, 1cm was scraped with a spatula3The activated carbon powder of (2) was spread on a microscope slide and pressed under a pressure of 1bar to prepare a surface as flat as possible. Then, a Drop of deionized water having a volume of 10. mu.L was dropped on the powder surface using Easy Drop. The contact angle between the water droplet and the powder was measured using a droplet shape analysis DSA1 software using the tangent method with system water. The contact angle value was measured to be 15 ° after 5s of water dropping on the activated carbon surface, indicating that the hydrophilicity of the material was good.
Example 2
Weighing 15g of trimeric cyclophosphazene and 100g of petroleum coke, performing ball milling pre-dispersion, crushing a pre-dispersion mixture to obtain a particle size D50 of 25 mu m by using a jet mill, mixing the crushed material with an activator zinc chloride according to a mass ratio of 1:4, heating to 650 ℃ in an activation furnace with nitrogen protection after uniform mixing, performing activation treatment for 4 hours, cooling to room temperature after reaction is finished, removing the activator and impurities in the obtained carbon material by using dilute hydrochloric acid, washing to be neutral by using deionized water, and drying after washing to obtain the nitrogen-phosphorus co-doped activated carbon.
The nitrogen and phosphorus co-doped activated carbon prepared in example 2 of the present invention was characterized.
Referring to fig. 2, fig. 2 is an SEM scanning electron micrograph of the nitrogen and phosphorus co-doped activated carbon prepared in example 2 of the present invention.
BET test is carried out on the doped active carbon, and the result shows that the specific surface area of the co-doped active carbon is 1800m2/g。
XPS test is carried out on the doped active carbon, and the mass percent of nitrogen atoms and phosphorus atoms doped in the co-doped active carbon is 2.78%, and 5.14%.
The nitrogen and phosphorus co-doped activated carbon prepared in example 2 of the invention is subjected to electrochemical performance detection.
Weighing the multi-element co-doped active carbon prepared in the embodiment, a conductive agent and a binder according to a mass ratio of 8:1:1, uniformly mixing, dripping isopropanol in a mortar grinding process until the mixture is pasty and has no dry powder, coating the mixture on a titanium sheet current collector, drying the titanium sheet current collector for 6 hours in vacuum at 120 ℃ to be used as a working electrode, wherein the auxiliary electrode is 1 × 1cmPt, and the reference electrode is Hg/Hg2SO4Electrode and electrolyte are 5mol/LH2SO4And carrying out LSV test on the three-electrode system by adopting a Zahner electrochemical workstation, wherein the LSV test scanning speed is 10mV/s, and the voltage window is-1.35 to-0.5V.
According to LSV curve analysis, the hydrogen evolution potential of the activated carbon prepared in parallel without doping with the same raw material is-0.85V, and when the potential is-1.35V, the hydrogen evolution current density of the activated carbon prepared in parallel without doping with the same raw material is 8.46A/g; the hydrogen evolution potential of the nitrogen and phosphorus co-doped active carbon prepared in the above embodiment is shifted from minus 0.85V to minus 1.09V, and the hydrogen evolution current density at minus 1.35V is obviously reduced to about 0.684A/g, which indicates that the nitrogen and phosphorus co-doped active carbon prepared in the above embodiment has an obvious hydrogen evolution inhibition effect.
Other performance tests are performed on the nitrogen-phosphorus co-doped activated carbon prepared in the embodiment 2 of the invention.
The conductivity of the activated carbon was 50S/cm as measured by a powder resistance meter.
The wettability of the activated carbon is tested by testing a contact angle, and the specific method comprises the following steps:
at 20 deg.C, 1cm was scraped with a spatula3The activated carbon powder of (2) was spread on a microscope slide and pressed under a pressure of 1bar to prepare a surface as flat as possible. Then, a Drop of deionized water having a volume of 10. mu.L was dropped on the powder surface using Easy Drop. The contact angle between the water droplet and the powder was measured using a droplet shape analysis DSA1 software using the tangent method with system water. The contact angle value was 10 ° after 5s of water dropping on the activated carbon surface, and the hydrophilicity of the material was good.
Example 3
Weighing 10g of hexafluorocyclotriphosphazene and 100g of coconut shell, performing ball milling pre-dispersion, crushing the pre-dispersion mixture to obtain a particle size D50 of 25 microns by using a jet mill, mixing the crushed material with an activating agent sodium hydroxide according to a mass ratio of 1:2, heating to 750 ℃ in an activating furnace with nitrogen protection after uniform mixing, performing activation treatment for 1.5 hours, cooling to room temperature after reaction is finished, removing the activating agent and impurities in the obtained carbon material by using dilute hydrochloric acid, washing to be neutral by using deionized water, and drying after washing to obtain the nitrogen-phosphorus-fluorine co-doped activated carbon.
The nitrogen-phosphorus-fluorine co-doped activated carbon prepared in example 3 of the present invention was characterized.
Referring to fig. 3, fig. 3 is an SEM scanning electron micrograph of the nitrogen and phosphorus co-doped activated carbon prepared in example 3 of the present invention.
The BET test is carried out on the doped activated carbon, and the result shows that the specific surface area of the doped activated carbon is 1500m2/g。
XPS test is carried out on the doped active carbon, and the mass percent of nitrogen atoms, phosphorus atoms and fluorine atoms doped in the co-doped active carbon is 1.72%, 3.74% and 4.47%.
The nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the embodiment 3 of the invention is subjected to electrochemical performance detection.
Weighing the multi-element co-doped active carbon prepared in the embodiment, a conductive agent and a binder according to a mass ratio of 8:1:1, uniformly mixing, dripping isopropanol in a mortar grinding process until the mixture is pasty and has no dry powder, coating the mixture on a titanium sheet current collector, drying the titanium sheet current collector for 6 hours in vacuum at 120 ℃ to be used as a working electrode, wherein the auxiliary electrode is 1 × 1cmPt, and the reference electrode is Hg/Hg2SO4Electrode and electrolyte are 5mol/LH2SO4And carrying out LSV test on the three-electrode system by adopting a Zahner electrochemical workstation, wherein the LSV test scanning speed is 10mV/s, and the voltage window is-1.35 to-0.5V.
According to LSV curve analysis, the hydrogen evolution potential of the activated carbon prepared in parallel without doping with the same raw material is-0.85V, and when the potential is-1.35V, the hydrogen evolution current density of the activated carbon prepared in parallel without doping with the same raw material is 8.46A/g; the hydrogen evolution potential of the nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the above embodiment is shifted from minus 0.85V to minus 1.14V, and the hydrogen evolution current density at minus 1.35V is obviously reduced to about 0.582A/g, which indicates that the nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the above embodiment has an obvious hydrogen evolution inhibition effect.
Other performance tests are performed on the nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the embodiment 3 of the invention.
The conductivity of the activated carbon was 80S/cm as measured by a powder resistance meter.
The wettability of the activated carbon is tested by testing a contact angle, and the specific method comprises the following steps:
at 20 deg.C, 1cm was scraped with a spatula3The activated carbon powder of (2) was spread on a microscope slide and pressed under a pressure of 1bar to prepare a surface as flat as possible. Then, a Drop of deionized water having a volume of 10. mu.L was dropped on the powder surface using Easy Drop. The contact angle between the water droplet and the powder was measured using a droplet shape analysis DSA1 software using the tangent method with system water. The contact angle value was determined to be 0 ° after 5 seconds of water dripping onto the activated carbon surface, and the hydrophilicity of the material was good.
Example 4
Weighing 5g of pentafluoroethoxy cyclotriphosphazene and 100g of phenolic resin, performing ball milling pre-dispersion, crushing the pre-dispersion mixture to obtain a particle size D50 of 25 micrometers by using a jet mill, mixing the crushed material with an activating agent potassium hydroxide according to a mass ratio of 1:5, heating to 750 ℃ in an activating furnace with nitrogen protection after uniform mixing, performing activation treatment for 1h, cooling to room temperature after reaction is finished, removing the activating agent and impurities in the obtained carbon material by using dilute hydrochloric acid, washing to be neutral by using deionized water, and drying after washing to obtain the nitrogen-phosphorus-fluorine co-doped activated carbon.
The nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the embodiment 4 of the invention is characterized.
The BET test of the doped activated carbon shows that the specific surface area of the doped activated carbon is 2300m2/g。
XPS test is carried out on the doped active carbon, and the mass percent of nitrogen atoms, phosphorus atoms and fluorine atoms doped in the co-doped active carbon is 1.58%, 3.51% and 3.58%.
The nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the embodiment 4 of the invention is subjected to electrochemical performance detection.
Weighing the multi-element co-doped active carbon prepared in the embodiment, a conductive agent and a binder according to a mass ratio of 8:1:1, uniformly mixing, dripping isopropanol in a mortar grinding process until the mixture is pasty and has no dry powder, coating the mixture on a titanium sheet current collector, drying the titanium sheet current collector for 6 hours in vacuum at 120 ℃ to be used as a working electrode, wherein the auxiliary electrode is 1 × 1cmPt, and the reference electrode is Hg/Hg2SO4Electrode and electrolyte are 5mol/LH2SO4And carrying out LSV test on the three-electrode system by adopting a Zahner electrochemical workstation, wherein the LSV test scanning speed is 10mV/s, and the voltage window is-1.35 to-0.5V.
According to LSV curve analysis, the hydrogen evolution potential of the activated carbon prepared in parallel without doping with the same raw material is-0.85V, and when the potential is-1.35V, the hydrogen evolution current density of the activated carbon prepared in parallel without doping with the same raw material is 8.46A/g; the hydrogen evolution potential of the nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the above embodiment is shifted from minus 0.85V to minus 0.98V, and the hydrogen evolution current density at minus 1.35V is obviously reduced to about 0.947A/g, which indicates that the nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the above embodiment has an obvious hydrogen evolution inhibition effect.
Other performance tests are performed on the nitrogen-phosphorus-fluorine co-doped activated carbon prepared in the embodiment 4 of the invention.
The conductivity of the activated carbon was 70S/cm as measured by a powder resistance meter.
The wettability of the activated carbon is tested by testing a contact angle, and the specific method comprises the following steps:
at 20 deg.C, 1cm was scraped with a spatula3The activated carbon powder of (2) was spread on a microscope slide and pressed under a pressure of 1bar to prepare a surface as flat as possible. Then, a Drop of deionized water having a volume of 10. mu.L was dropped on the powder surface using Easy Drop. The contact angle between the water droplet and the powder was measured using a droplet shape analysis DSA1 software using the tangent method with system water. The contact angle value was determined to be 0 ° after 5 seconds of water dropping on the activated carbon surface, indicating that the hydrophilicity of the material was good.
Comparative example 1
Weighing 100g of petroleum coke, performing ball milling pre-dispersion, crushing the pre-dispersion mixture to a particle size D50 of 15 microns by using a jet mill, mixing the crushed material with an activating agent potassium hydroxide according to a mass ratio of 1:2.5, heating to 800 ℃ in an activating furnace with nitrogen protection after uniform mixing, performing activation treatment for 1h, cooling to room temperature after reaction is finished, removing the activating agent and impurities in the obtained carbon material by using dilute hydrochloric acid, washing with deionized water to be neutral, and drying after washing to obtain the petroleum coke-based activated carbon.
The activated carbon prepared in comparative example 1 of the present invention was characterized.
The BET test is carried out on the activated carbon, and the result shows that the specific surface area of the co-doped activated carbon is 1000m2/g。
The petroleum coke-based activated carbon prepared in comparative example 1 of the invention was subjected to electrochemical performance detection.
Weighing the petroleum coke-based activated carbon prepared in the embodiment, a conductive agent and a binder, uniformly mixing according to a mass ratio of 8:1:1, dripping isopropanol in the process of grinding in a mortar until the mixture is pasty and free of dry powder, coating the mixture on a titanium sheet current collector, drying in vacuum at 120 ℃ for 6 hours to be used as a working electrode, wherein the auxiliary electrode is 1 × 1cmPt, and the reference electrode is Hg/Hg2SO4Electrode and electrolyte are 5mol/LH2SO4And carrying out LSV test on the three-electrode system by adopting a Zahner electrochemical workstation, wherein the LSV test scanning speed is 10mV/s, and the voltage window is-1.35 to-0.5V.
According to LSV curve analysis, the hydrogen evolution potential of the petroleum coke-based activated carbon is-0.85V, and when the potential is-1.35V, the hydrogen evolution current density of the petroleum coke-based activated carbon is 8.46A/g. The conductivity of the activated carbon was 0.5S/cm as measured by a powder resistance meter.
The wettability of the activated carbon is tested by testing a contact angle, and the specific method comprises the following steps:
at 20 deg.C, 1cm was scraped with a spatula3The activated carbon powder of (2) was spread on a microscope slide and pressed under a pressure of 1bar to prepare a surface as flat as possible. Then, a Drop of deionized water having a volume of 10. mu.L was dropped on the powder surface using Easy Drop. The contact angle between the water droplet and the powder was measured using a droplet shape analysis DSA1 software using the tangent method with system water. Determination after 5s of water dripping on the surface of the activated carbonThe contact angle value was 75 deg., indicating that the material was less hydrophilic.
The multi-element co-doped activated carbon composite material for the negative electrode of the lead-carbon battery, the preparation method thereof and the lead-carbon battery provided by the invention are described in detail, specific examples are applied in the description to explain the principle and the embodiment of the invention, and the description of the examples is only used for helping to understand the method and the core idea of the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any device or system and implementing any combined method. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. The multi-element co-doped active carbon composite material is characterized by comprising active carbon and hydrogen evolution inhibiting heteroatoms doped on the active carbon;
the hydrogen evolution inhibiting heteroatoms are two or three of N, P and F;
the hydrogen evolution inhibiting heteroatom is provided by a heteroatom compound.
2. The composite material according to claim 1, characterized in that the heteroatom compound is a nitrogen-containing phosphorus compound and/or a fluorine-containing nitrogen-phosphorus compound;
in the composite material, the mass percentage of the nitrogen atoms is 0.1-10%;
in the composite material, the mass percentage of the phosphorus atoms is 0.1-10%;
in the composite material, the mass percentage of the fluorine atoms is 0.1-10%.
3. The composite material according to claim 1, characterized in that the heteroatom compound is a phosphazene-based compound;
the composite material is obtained by activating a precursor of activated carbon and a heteroatom compound;
the particle size of the multi-element co-doped active carbon composite material is 5-50 mu m;
the specific surface area of the multi-element co-doped active carbon composite material is 500-1500 m2/g。
4. The composite of claim 3, wherein the heteroatom compounds comprise one or more of hexamethylcyclotriphosphazene, cyclotriphosphazene, hexamethoxycyclotriphosphazene, hexaethoxycyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene, and pentafluorophenoxycyclotriphosphazene;
the hydrogen evolution inhibiting hetero atoms are doped on the surface of the activated carbon and are uniformly doped in pore channels of the activated carbon;
the precursor of the activated carbon comprises one or more of petroleum coke, biomass and resin;
the multi-element co-doped active carbon composite material has a hydrogen evolution current density of 0.5-1.5A/g when the hydrogen evolution potential is-0.9V.
5. The composite of claim 1, wherein the heteroatom compound comprises hexamethylcyclotriphosphazene, cyclotriphosphazene, hexamethoxycyclotriphosphazene, hexaethoxycyclotriphosphazene, hexafluorocyclotriphosphazene, pentafluoroethoxycyclotriphosphazene, or pentafluorophenoxycyclotriphosphazene;
the mesoporous volume of the multi-element co-doped active carbon composite material is 50-80%;
the contact angle of water drops of the multi-element co-doped active carbon composite material is less than or equal to 15 degrees;
the conductivity of the multi-element co-doped active carbon composite material is more than or equal to 50S/cm.
6. The preparation method of the multi-element co-doped active carbon composite material is characterized by comprising the following steps of:
1) grinding and mixing the activated carbon precursor and the heteroatom compound to obtain a mixed material;
2) and mixing the mixed material obtained in the step with an activating agent again, and activating under the condition of protective gas to obtain the multi-element co-doped active carbon composite material.
7. The method of claim 6, wherein the milling and mixing comprises ball milling and dispersing;
the grinding and mixing time is 0.5-2 h;
the rotation speed of the grinding and mixing is 100-800 r/min;
the mass ratio of the heteroatom compound to the activated carbon precursor is 1: (5-30).
8. The method of claim 6, further comprising a jet milling step after the mixing;
the activator comprises one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide and zinc chloride;
the mass ratio of the activating agent to the activated carbon precursor is (1-6): 1.
9. the preparation method according to claim 6, wherein the remixing time is 0.5-2 hours;
the activation temperature is 400-800 ℃;
the activation time is 1-6 h;
a post-treatment step is also included after the activation;
the post-treatment step comprises one or more of impurity removal, filtration, washing and drying.
10. A lead-carbon battery is characterized by comprising a positive electrode and a negative electrode;
the cathode comprises the multielement co-doped active carbon composite material disclosed by any one of claims 1-5 or the multielement co-doped active carbon composite material prepared by the preparation method disclosed by any one of claims 6-9.
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